Manufacture of detergents



Patented Mars 23,

orrlc 2,438,169 MANUFACTURE OF EETERGEN'ES Lester Francis Hoyt,

to Allied Chemical York, N.Y.,

No Drawing.

East Aurora,

8: Dye Corporation, acorporat N. 2., assignor New ion of New YorkApplication duly 12, 1945,

Serial No. 604,731

1! Claims. (01- 252-=-=121)' This invention relates to improvements inthe manufacture of detergents, more particularly milled soaps andespecially milled soapsO! the type employed for toilet purposes. Itrelates to improvements in milled soap compositions containing a hardsoap and a synthetic detergent of the higher petryl sultan-ate type andespecially of the higher petryl aromatic sulionate type, and toimprovements inthe processes of manufacturing milled soaps containing ahard soap and a synthetic detergent of the higher petryl sulionate typeand especially of the higher petryl aromatic sulfonate type.

As employed throughout this specification and claims, the term soapdenotes and includes the water-soluble ganic amine salts or" higherfatty 10 to 20 carbon atoms; the term "hard soap" denotes and includesthose "soaps which Iorm solid masses under normal atmosphericconditions; and the terms higher petryl sulionate" and higher petrylaromatic sulionate denote and include mixtures of organic sulionates andsubstituted aromatic sulionates, respectively, in which an organicradical which is part of the organic sulfonate, or which is asubstituent in the aromatic nucleus oi the aromatic sulionate, isderived irom a polycomponent hydrocarbon mixture of the type of apetroleum distillate (a petroleum distillate or a synthetic mixturewhose composition is similar to a petroleum distillate) boiling for themost part Within the range 100 to 300 C. at atmospheric pressure. suchsoaps are the sodium, potassium, ammonb um, and triethanolamine salts ofsaturated and unsaturated higher fatty acids derived from coconut oil,palm oil, olive oil, tallow, cottonseed oil, and the like, and. mixturesthereof, well known to those skilled in the soap-making art. Detergentsof the higher petryl aromatic sulfonate type are disclosed, for example,in United States Patents 2,196,985; 2,218,472; 2,220,099; 2,223,364;2,233,- 408; 2,267,725; 2,364,782; and British Patent e16,- 379. Otherexamples of detergents of the higher petryl sulfonate type are petroleumsulfonates obtained in the refining of lubricating oils, and sulionatedproducts obtained by treating mineral oil fractions by the process ofUnited States Reissue Patent No. 20,968 and United States Patents Nos.2,197,800; 2,202,791; 2,239,974; and 2,276,090.

It is known to produce soap compositions containing a hard soap and ahigher petryl sulionate for use as effective detergents and washingagents in water of varying degrees hardness, and in acids contaiExamples of sea water.

alkali metal, ammonium, and orv Such com ositions have been prepared,for example, by mixing a higher petryl aromatic sulionate with moltenkettle soap in a crutcher, allowing the resulting mixture to cool andsolidify in frames, and cutting the resulting solid soap compositioninto bars or cakes.

A. milled soap cannot be prepared from the result framed soapcompositions because the high content of water present in saidcomposititans (30% or more) renders them .soft and mushy, so thatplodding cannot be satisfactorily effected. Preparation of a milled soapproduct by mixing a hard soap in a form usually employed for milling (e.g. in the form of ribbons, beads, particles, flakes, grains, or thelike, containing 5% to 15% .oi'moisture) with a higher petryl sulionatein a substantial amount le. g. 15% of the weight of the soap) presentsdifilcultles; the mixture becomes sticky and tough so that it opposesmilling and plodding in the usual commercial soap-making equipmen. If itis attempted to improve the plasticity of such mixture by the additionof water, the mixture merely becomes more tacky and its workingproperties are not materially improved. In View of these difllculties,heretofore the manufacture of soap bars and cakes containing mixturesoisoap and higher petryl sulionates has been largely restricted toframed soap products.

According to the present invention, the production oi milled soapscontaining a hard soap and a higher petryl sulfonate can be efiectivelycarried out in the ordinary soap-making equipment and with the use ofcommercially available higher petryl sulfonate detergents, byincorporating a substantial amount soluble form, into a mixture of thehigher petryl sulionate and hard soap containing moisture. In accordancewith the present invention, it has been found that the presence ofstarch in the insoluble form serves to overcome the stickiness andtoughness of the composition, with the result that the mixtures flowreadily through the plodder without requiring greater pressure than isnormally employed in the manufacture of the usual milled toilet soaps,and the resulting bars issuing from the plodder are smooth and lightcolored. Further, the presence of the starch in the resulting soapproducts imparts a satiny feel to the products.

Corn starch is ordinarily employed, because of its low cost and generalavailability, but any other water-insoluble starch may be used; such as,wheat starch, tapioca starch, potato starch, etc. The starch is presentin the novel compositions of starch, in the ordinary inand milled barsor cakes essentially in the form 01' unruptured, insoluble particles.

and other inorganic salts present in the mixture, and the use to whichthe product is to be put. In general, the amount of starch should be atleast suiiicient to provide compositions which may be milled and ploddedwithout dificulty in the usual of the bars or find that soap-higherpetrylbenzene sulionate-starch mixtures of the type of the presentinvention containing as high as 40% by weight of starch will yieldmilled bars possessing a feel and mixtures is as low as 25%.

As employed herein, the expression "total weight of basic componentsrefers to the sum hydrous, inorganic-sait-free basis), (3) starch (on ananhydrous basis), and (4). if present, sodium sulfate and/or otherinorganic salts.

In preparing the milled soaps in accordance with the present invention,the hard soap, in the form of ribbons, flakes, beads, or other formcommonly employed for making milled soaps, is mixed with a higher petrylsulfonate and starch in suitable mixing apparatus, such as a soap mill,and the resulting mixture is introduced into a stamped or otherwiseconverted into the desired form. As in usual in the mixtures containwater, which is ordinarily introduced in the form of moisture present inthe soap. The amount of water preferably should not exceed of the abovetotal weight of basic components. Greater amounts 01 moisture render thecomposition too soft for satisfactory working, Preferably, the mixturescontain an amount of water equal to at least 6% of the total weight ofbasic components," to provide desirable working properties. In general,amounts of water equal to 10% to 12% of the total weight of basiccomponents" upon the uses to which the resulting products are to be put.In general, an amount of higher petryl the making of milled soaps;

4 sulionate (on an anhydrous, basis) equal to at least 6%, preferably atleast of the total weight of :basic components" For use in waterinorganic-salt-free with the use of the products in sea water, such aminimum ount of soap is desirable to pro= vide the products withadvantageous washing ability in sea water.

Within these limits, the proportio example, in tallow soap, or othertoilet employed in making milled and about 20% (mainly sodium sulfate),the proportions of ingredients (in terms to about 40% of inorganic saltsof 100 parts of the total weight of the three com ponents on ananhydrous basis) may be as follows:

I Component: Parts sodium higher petryi benzene sulfo nate composition20 to to ap 15 to 55, preferably 25 to Starch" 5 to 40, preferably 20 to30 Another commercially available higher petryl benzene sulfonatecomposition, containing about 95% to about of a sodium higher petrylbenzene sulfonate derived from a kerosene frac- 5% to about 15% ofComponent:

Sodium higher petryl nate composition- Parts 10 to 40 30 to 80,preferably 40 to 70 Starch 5 to 40, preferably 20 to 30 Other forms ofcommercially available higher petryl sulfonates may be employed, anumber of which are disclosed in the patents above referred to, Ofthese, the higher petryl aromatic sulfonates are preferred.

The higher petryl aromatic sulfonates are mixbenzene sulfotures ofsubstituted derivatives of aromatic sulreferred to as wherein Arepresents is hydrogen or droxy-alkyl ammonium,

petroleum distillate. and preferably of mineral origin, of which atleast 80% boils (distills) between 150" and 250 C. (Ranges herein statedinclude the limits. The term a poly-component non-aromatic hydrocarbonmixture" as employed herein, means a hydrocarbo petroleum or a petroleumdistillate or otherwise refined petroleum fraction, or other mixture ofsimilar composition, containing straight and/or branched chain alkanesand which may also contain cycloalkanes and aryl hydrocarbons but doesnot contain more than 20% of aryl hydrocarbons. For convenience,stituted derivatives of aromatic sulfonates are mixtures of alkylaromatic sulfonates," the term "alky being used in its broad sense toinclude straight or branched, open-chain aliphatic hydrocarbon radicals,as well as radicals derived from cyclophatic and aromatic-aliphatichydrocarbons which may be present in the polycomponent hydrocarbonmixture).

They are mixtures of water-sigluble products represented by the generalformul son! an aromatic nucleus preferably containing not more than twobenzene nuclei which may be condensed or not (for example, a benzenenucleus. a naphthalene nucleus, a diphenyl nucleus, or a diphenyl oxidenucleus); R represents an alky group which is directly attached to acarbon atom of the nucleus represented by A and which is derived fromthe hydrocarbon mixture and corresponds with a component thereof; Xrepresents a replaceable hydrogen of the aromatic nucleus represented bA or a substituent such as an allryl group containing 1 to 8 carbonatoms, a hydroxyl group, an alkoxy or aralkoxy group containing 1 to 8carbon atoms, or halogen; n represents the numbers 1, 2 or 3; and SOaYrepresents a sulfonate group which is attached to a carbon atom of thearomatic nucleus represented by A andin which Y its stoichiometricequivalent of a salt-forming metal or radical; such as sodium,potassium, ammonoum, alkyl ammonium, hy-

and the like. Thus the mixtures of higher petryl aromatic sulfonates maybe derived from benzene, toluene, xylene, phenol, cresol, anisole,phenetole. chlorbenzene, diphen l, hydroxydiphenyl, diphenyl oxide,naphthalene, alpha-naphthol, beta-naphthol, etc. Those derived frommononuclear aromatic compounds, and especially benzene, are preferred.Ordinarily the sodium salts are prefei'red b reason of their lower cost.

Preferably, they are mixtures obtained by a process comprisingchlorinating the polycomponent hydrocarbon mixture to form mixed alkylchlorides, condensing resulting mixed alkyl chlorides with a mononucleararomatic hydrocarbon or a derivative thereof to produce a mixture ofalkyl derivatives of said aromatic hydrocarbon or derivative, andsulfonating a mixture of said alkyi derivatives.

The following example illustrates the preparation of such a higherpetryl benzene sulfonate by such a process. The parts are-by weight:

Exsmta A A Pennsylvania kerosene boiling from 180 C. to 280 C., 80% ofwhich boiled between 190 and 255 0., was chlorinated between 70 and 75until the n mixture, such as the mixture of subspecific gravity of thelatter had increased from 0.788 at 24 C. to 0.918 at 24 C. 10 parts ofthe resulting chlorinated kerosene were introduced during 75 minutesinto a mixture of 20 parts of benzene and 0.5 part of aluminum chloride,while gradually raising the temperature to 45 C., after which themixture was agitated at 45 C. for 15 minutes and then allowed tostratify. The upper layer of oil was removed from the tarry lower layerand distilled, and the fraction which boiled between and 240 C. at 3 to"1 mm. of mercury absolute pressure was collected separately. Thecollected fraction was refined by agitating it with 18.4% of its weightof sulfuric acid at about 40 C. for 30 to 40 minutes, allowing the massto settle 30 minutes, and discarding the lower acid layer. The refined011 was mixed with 1.35 times its weight of 100% sulfuric acid at 30 0.,the mixture was warmed to 55 to 60 C., agitated at that temperature for1 hour and allowed to stratify for 4hours, and the lower layer was drawnoil. The remainder containing higher petryl benzene sulfonic acid wasrendered neutral to Nitrazine Yellow paper by stirring it into about oneand one-half times its. weight of water simultaneously with 50% aqueouscaustic soda. To the neutralized mass, which contained about 35% ofinorganic salt (mostly sodium sulfate) and about 65% of sodium higherpetryl benzene sulfonate on a dry basis, sufficient sodium sulfate wasadded to give a dry composition containing 60% of sodium keryl benzenesulfonate. and the resulting mixture was drum dried.

In addition to the essential components above referred to, othersubstances usually incorpo rated in milled soaps may be included in thecompositions of the present invention. Thus, perfumes, pigments,coloring agents, antiseptics, and the like may be incorporated into thecompositions. In general, it is preferred not to have considerableamounts of such substances in the compositions.

Inorganic salts, chiefly sodium sulfate, which are frequently present incommercial forms of higher petryl sulfonates, may be included in thecompositions of invention; but the amount of inorganic and preferablyshould not exceed 20%. total weight of basic components.

Further, substances imparting supplementary surface activity to theabove essential components of higher petryl sulfonate is relativelysmall; for example, lower alkyl aromatic sulfonates, and particularlysodium isopropyl naphthalene suifonate. sodium di-isopropyl naphthalenesulfonate, sodium butyl naphthalene sulfonate.

The ingredients may be mixed and converted into bar form in any suitableequipment. Thus, the mixture may be milled, plodded and stamped inapparatus commonly used for manufacturing high-grade toilet soaps. Wherehighly comminuted compositions are employed, relatively little millingmay achieve the desired degree of homogeneity, and such compositions maybe formed directly into bars by passage through a plodder, which itselfprovides some milling action.

To promote easy working, it is helpful to warm 90 to F. Suchtemperatures may be developed in part or completely by the friction ofthe milling and plodding action. The shaping die of the plodder may beheated, say to about F., to facilitate the ex- 40% of inorganic saltsand about going manner, showed better ataamo trusion of the compositionin the form of a smooth bar. The resulting bars may be cut and stampedto suitable size and shape.

The following examples illustrate the invention. The parts are byweight. The corn starch used was "Argo edible corn starch and containedabout of moisture.

Example 1 A mixture of 420 parts of powdered corn starch, 515 parts of"S soap (a pure soap of 39 titre sold by John Powell and Company, Inc.,New York city), adjusted to contain 110 parts of moisture, and 675 partsof the product of Example A (a sodium higher petryl benzene sulfonatedetergent containing about 40% of sodium sulfate and about 60% ofasodium higher petryl benzene sulfonate derived from a, kerosene fracordoughinessfi' was of a Houchin soap plodder. The mixture flowed into theplodder desired form in a stamping machine, did not sweat on exposure tothe atmosphere, or frost," disintegrate or become soft in use, andlathered and washed well in water of positions employing starch.

The following examples illustrate additional soaphigher petrylsulfonate-starch mixtures which, in accordance with this invention, whenmilled and plodded into bar form in the forepossessed good firmness andappearance, and did sweat, frost, disintegrate, or become soft in use.

Example 2 Parts "818 soap chips (a pure tallow soap of 41 titre sold byArmour & Company) adjusted to contain about 7 parts of moisture Sodiumhigher petryl benzene sulfonate detergent employed in Example 1 p 45Corn starch 28 Example 3 Parts "#818" soap chips adjusted to containabout a 7 parts of moisture 34 Detergent composition containingapproximately 8 parts of inorganic salts (mostly sodium sulfate) and 292parts of a mixture consisting of a sodium higher petryl m benzenesulfonate derived from a kerosene fraction of Pennsylvania petroleum(11.7 parts) and sodium di-lsopropylnaphthalene sulfonate (17.5 parts)45 Cornstarch 28 15 Example 4 Pa #818 soap chips adjusted to containabout 9 parts of moisture go Sodium higher petryl benzene sulfonatedetergent employed in Example 1 40 Corn starch Example 5 25 Parts #818soap chips adjusted to contain about.

8 parts of moisture 23 Sodium higher petryl benzene sulfonate de-.tergent employed in Example 1 60 a0 Corn starch 25 Example'ti Parts #818soap chips adjusted to contain about 10 parts of moisture 55 Sodiumhigher petryl benzene sulfonate detergent employed in Example 1 45 Cornstarch 10 40 Example 7 Parts "Harris soap chips (10% coconut oil soapand 90% tallow soap) containing about 10 parts of moisture 60 Sodiumhigher petryl benzene sulfonate detergent containing about 10% ofinorganic salts (mostly sodium sulfate) and about 90% of a sodium higherpetryl benzene sulfonate derived from a kerosene fraction ofPennsylvania petroleum 25.5 Corn starch 22.5

Example 8 Parts Lux" soap flakes adjusted to contain about 9 parts ofmoisture 45 Detergent composition containing approximately 9.1 parts ofinorganic salts (mostly sodium sulfate), and 27.4 parts of a mix-' tureconsisting of a sodium higher petryl benzene sulfonate derived from akerosene fraction of Pennsylvania petroleum (11 5 parts) and sodiumdi-isopropylnaphtha-r lene sulfonate (1,6.4 parts) 36.5 Corn starch 26Example 9 P #818 soap chips adjusted to contain about 10 parts ofmoisture 1 52 Sodium higher petryl benzene sulfonate detergent employedin Example 7 32 Corn starch 25 Toilet soap stock adjusted to containabout Example 11 Parts Toilet soap stock adjusted to contain about '7parts of moisture Sodium higher petryl benzene sulionate detergentemployedin Example 'l Corn starch 11 Titanox (titanium oxide Example 12Parts 8 parts of moisture tergent employed in Example 1 29 Corn starch30 Example 13 Parts Toilet soap stock adjusted to contain about parts ofmoisture Sodium higher petryl benzene sulionate detergent employed inExample 1..-; 29 Corn starch 26 Example 14 Parts Toilet soap stockadjusted to contain about 10 parts of moistur 52 Sodium higher petrylbenzene sulionate detergent employed in Example 1 25 Corn stare 25Example 15 Parts Toilet soap stock adjusted to contain about 10 parts ofmoisture Sodium higher petryl benzene sulionate detergent employed inExample 1 35 Corn starch Example 16 Parts Toilet soap stock adjusted tocontain about 9 parts of moisture Sodium higher petryl benzene sulionatedetergent employed in Example 1 40 Corn starch 2'7 It will be realizedby those'skilled in the art that the invention is not limited specificexamples and that changes may be made in the compositions and processesof preparing them, within the scope or the appended patent claims.

Thus, instead or the specific components employed in the above examples,others oi the substances referred to above may be substituted in equalamounts. I tional substances may be incorporated into the compositionsbesides the essential components: a. hard soap, a higher petrylsulfonate, and starch.

As above noted, the alt employed amount of s relative to the amount of.higher petry-l sultonate to the above Y will depend upon severalfactors, one oi which is sodium other inorganic salts present in thehigher petryl sultonate or otherwise sition subjected to milling. In 8amount or soap is reduced to compensate for the amount or sodium sulfateand/or other inorganic salts present in the composition.

Thus, in accordance with the present invention, the compositionssubjected to milling may contain the following components: (1) a hardsoap, (2) a higher petryl suiionate, and 3) starch, together with (4)inorganic salt in an amount ranging from 0% to 25% of the wei htv oi theadmixture, in the following proportions by weight ofsaid componen (l),(2), and (3). on the basis of a total weight of 100 parts 02 said fourcomponents:

In this case, the minimum amount of soap is 15 parts by weight,

and the maximum amount is 5 parts by weight less the weight of inorganicsalt. i

Or, in the case 01 preferred compositions containing the followingcomponents: (1) a hard soap,

(2) a higher petryl aromatic sulfonate. and (3) starch, together with(4) sodium sulfate in an amount ranging from to 20% of the weight of theadmixture, the proportions by weight of said components (1) (2) and (3)on the basis of a total weight or 100 parts or said tour components, maybe within the following ranges:

Parts sulfonate...... at least 10 30 to 80, less the weight of sodiumsulfate amount of soap may vary by weight, minus the weight of the byWeight, minus the In this instance, the from '30 parts sodium sulfate,to parts weight of sodium sulfate.

1'. claim:

1. In the manufacture oi a milled soap from a mixture comprising waterand at least the following components: ii) a soap which forms solidmasses under normal atmospheric conditions and which is selected fromthe group consisting of the alkali metal, ammonium, and organic aminesalts 02 higher fatty acids containing ill to as carbonatoms, and (2) ahigher petryl sulionate, the improvement which comprises incorporating(3) starch into a mixture of said type containing an (4) inorganic saltranging from 0% to mixture, milling and Component:

Soap

' Parts to (-1!) where X equals the weight of inorganic salt Higherpetryl sulfonatei. at least Starch -4 5 to 40 and limiting the amount-oiwater-in said mixture to 6 to 15 parts per "parts of the total weight ofcomponents (1), (2), (3), and (4).

(1), (2), and (3) So that l Component:

Component: Parts Soap to (85X), where X equals the W i ht of sodiumsulfate Higher petryl sulfonate at least 10 Starch 10 to and limitingthe amount of water in said mixture to 6 to 15 parts per 100 parts ofthe total weight of components (1), (2), (3), and (4).

3. In the manufacture of a milled soap from a mixture comprising waterand at least the following components: (1) a soap which forms solid ahigher petryl aromatic sulfonate, milling and plodding the resultingmixture: and controlling the workability of the mix- Parts Soap 15 to(85X), where X equals the weight of sodium sulfate 7 Higher petrylaromatic sulfonate at least6 Starch and limiting the amount of water inSaid mixture to 6 to 15 parts per 100 parts of the total weight ofcomponents the plodded mixture into bars.

' 4. In the manufacture of a, milled soap from a I the mixture in themilling and plodding operations by proportioning the 12 amounts ofcomponents (1) (2), and (3) so that their relative weights, on the basisof a total weight of parts of components (1), (2), (3), and (4), liewithin the following ranges:

Component:

Soap 30 to 80, less the Weight of sodium sulfate Higher petryl aromaticsu11'onate at least 10 Starch ranges 1 Component:

Soap

- Parts 30 to 80, less the weight of sodium sulfate Higher petrylmononuclear aromatic sulfonate 6 to 40 Starch 10 to 40 and limiting theamount of water in said mixture to 6 to 15 parts per 100 parts of thetotal weight or the mixture; milling and plodding the resulting mixture:and controlling the workability nents (1), (2), weights, on the basis ofa total weight of 100 parts of components (1), (2), (3), and (4), liewithin the following ranges:

Component: Parts Soap 30 to 80, less the weight of sodium sulfate Higherpetryl benzene sulfonate 10 to 40 Sta 10 to 40 Parts said compositionmosaics Component:

Soap Sodium higher petryl benzene sulionate composition 20 to 60 Starch10 to 40 and limiting the amount of water in said mix:

ture to 6 to 15 parts per 100 parts of the total weight of saidcomponents (1), (2) and (3) 8. In the manufacture of a milled soap froma mixture comprising water and at least the following components: (1) asodium soap for toilet use and (2) a sodium higher petryl benzenesulfonate composition containing 95% its weight of sodium petryl benzeneof its weight of inorganic salts, the improvement which comprisesincorporating or said type; milling and plodding the resulting mixture;and controlling the workabi ity of the mixture in the milling andplodding operations by proporamounts or components (1), (2),

and (3), so that their relative weights, based on a total weight of 100parts of said components (1),

(2), and (3), lie within the following ranges:

Parts 15 to 55 Component: Parts Soap 30 to 80 Sodium higher etrylbenzene su fonate composition 10 to 40 Starch 5 to 40 and limiting theamount of water in said mixture to 6 to 15 parts per 100 parts of thetotal weight of said components (1), (2) ,and (3).

9. A milled soap composition comprising as its essential components: (1)a soap which forms solid masses under normal atmospheric conditions andwhich is selected from the group consisting Of the alkali metal,ammonium, and organic amine salts of higher fatty acids contain- (2) ahigher petryl sulionate. V together with (4) inorganic salt in 20% ofthe total weight of said four components, the proportions by weight ofsaid components (1) (2), and (3), on the basis of a total weight of 100parts of said four components, lying within the following ranges:

Parts 15 to (85-1!) where X equals the weight of inorganic salt Higherpetryl sulfonate at least 6 Starch 5 to 40 containing not more than 15the total weight Component Soap parts of water per 100 parts of of saidfour components.

10. A milled soap composition comprising as its essential components:(1) a soap which forms solid masses under normal atmospheric conditionsand which is selected from the group consisting of the alkali metal,ammonium, and organic amine salts of higher fatty acids contain ing 10to 20 carbon atoms, (2) a higher petryl sulfonate, and (3) starch,together with (4) sodiadapted um sulfate in an amount ranging 1mm 0% to20% or the total weight or said four components, weight of saidcomponents (1), (2) and (3). on the basis or a total weight of 100 partsoi said iour components, lying within the following ranges:

Parts soap 15 to (-1!) where X equals the weight 01 sodium sulfateHigher petryl sulionate at least 10 Starch 10 to 40 said compositioncontaining not more than 15 partsoi water per parts or the total weightof said four components.

11. A milled soap composition comprising as its essential components:(1) a soap which forms solid masses under normal atmospheric conditionsand which is selected rrom the group conthe alkali metal, ammonium, andorganic amine salts of higher fatty acids containpetryl (3) starch,together sulfate in an amount ranging or the total weight of said fourthe proportions by weight oi! said (1), (2), and (3), on the basis or aComponent:

aromatic sulionate, and with (4) sodium from 0% to 20% components.components total weight of 100 parts of said four components,

lying within Component:

Soap

the following ranges:

Parts 15 to (85-21), where X equals the weight of sodium sulfate Higherpetryl aromatic sulionate at least 6 Starch 5 to 40 said compositioncontaining not parts of water per 100 parts of the said four components.

12. A milled soap compositon comprising as its essential components: (1)asodium soap, (2) a higher petryl mononuclear aromatic sulfonate, and(3) starch, together with (4) sodium sulfate in an amount ranging from0% to 20% of the total weight of said four components, the proportionsby weight of said components (1) (2) and (3), on the basis of a totalweight of 100 parts of said iourcomponents, lying within the followingranges:

more than 15 total weight of Component: Parts Soap 30 to 80, less theweight of sodium sulfate Higher petryl mononuclear aromatic sniionate 10to 40 Starch: it to (it) said composition containing not more than 15parts of water per 100 parts of the total weight of said tourcomponents.

13. A milled soap composition comprising as its essential components:(1) a sodium soap adapted for toilet use, (2) a higher petryl aromaticsulfonate, (3) starch, and (4) an amount of sodium sulfate ranging from25% to 67% of the weight of the higher petryl aromatic sulfonate, theproportions by weight of said components (1), (2), and (3), on the basisor a total weight of 100 parts of said four components, lying within thefollowing ranges:

Component: Parts Soap 15 to 55 Higher petryl aromatic sulionate 20 to 60Starch 10 to 40 said composition containin not more than 15 15 parts orwater per 100 parts of the total weight of said four components.

14. A milled soap compositon comprising as its essential components (1)a sodium soap. (2) a nents: Component: Parts Soap 15 to 45 Sodium higherpetryl' benzene sulfonate detergent 40to 60 Starch 10 to 40 per 100 saidthree components.

15. A milled soap composition comprising'as its essential components (1)a sodium soap, (2) a said components (1) (2) and (3) on the a totalweight of 100 parts of said three components lying within the followingranges: Component: Parts Soap 5 to 45 Sodium higher petryl benzenesulfonate detergent-.- 20 to 60 Starch to 40 ,said compositioncontaining not more than parts of water per said three components.

16, A milled soap composition comprising as its essential said threecomponents lying ranges:

Component: P Soap 40 to Higher petryl aromatic sulionate detergent 10 to40 Starch 5 to 40 said composition containing not more than 15 parts ofwater per parts or the total weight of said three components.

lled soap composition comprising as its essential components: (1)

the proportions by weight of said components (1) (2), and (3) on thebasis of a total weight of 100 parts of said three components lyingwithin the following ranges: Component: Parts Soap 0 to 80 Sodium higherpetryl benzene suitonate detergent 19 to 40 Starch 5 to 40 parts ofwater per 100 parts of the total of said three components.

LESTER FRANCIS HOYT. REFERENCES CITED The following references are ofrecord in the file of this patent:

NITED STATES PATENTS OTHER REFERENCES Thomssen and Kemp (1937) Pages141-146 of Modern Soap Making, by

